Water-insoluble azo-dyestuffs and fiber dyed therewith



Patented July 28, 1936 UNIT. STAT WATER-INSOLUBLE AZO-DYESTUFFS AND FIBER DYED THEREWITH Oskar Haller, Ofienbach-on-the-Main, and Heinrich Morschel, Cologne-Deutz, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application March 11, 1935, Serial 12 Claims.

CONH- 7 wherein n means the number 1 or 2, R1 stands for a radical of the benzene, naphthalene, diphenyl or anthraquinone series and R2 stands for a radical of the benzene, naphthalene, diphenyl or carbazole series.

According to U. S. patent application Serial No. 10,582, filed March 11, 1935 by Oskar Haller and Heinrich Morschel for Arylides of 4-hydroxy-diphenyl-3-carboxylio acid, which application has matured into U. S. Patent No. 2,025,587, there may be obtained from 4-hydroxydipheny1- 3-carboxylic acid by condensation with arylamines according to known methods the 4-hydroxydiphenyl-3-carboxylic acid arylides.

Now, we have found that valuable azo-dyestuffs may be obtained by coupling the above mentioned 4-hydroxydiphenyl-3-carboxylic acidarylideswith diazo-, tetrazoor diazo-azo-compounds, only such components being used, as do not contain groups lending solubility, such as the sulfonic acid or carboxylic acid group. There are in most cases obtainedbrown and olive-green tints of good properties of fastness. The new dyestufis may be used for preparing pigment colors but preferably for dyeing fibers by the ice-color method or for printing fibers by one of the known printing processes.

The following examples serve to illustrate the invention but they are not intended to limit it thereto:

(1) 7 Cotton piece goods are impregnated on a foulard with a solution containing per liter 20 grams of 4-hydroxydiphenyl 3 carbonylaminobenzene 20 cc. of Turkey red oil and 40 cc. of caustic soda solution of 34 B.

and, after intermediate drying, developed in a solution containing per liter the diazo compound from 15.3 grams of 1-amino-2-(4'-chlorophenoXy)-5-chlorobenzene. The material is rinsed,

In Germany March 14, 1934 soaped and dried. A green-olive dyeing of very good fastness to light is obtained. The dyestufi has the following formula:

phenoXy-5-ohlorobenzene and 4-hydroxydiphen- 15 yl-3-carbonyl-(1' amino 4 chlorobenzene) a green olive, and with 4-hydroxydiphenyl-3-carbonyl-(1'-amino 2' methoxybenzene) a brownolive dyeing of likewise very good fastness to light are obtained. 2

(2) Well pre-treated cotton yarn is impregnated with a solution containing per liter 5 grams of bis-(4hydroxydiphenyl 3 carbonyl) 4=',4="diamino-3',3"-dimethoxydiphenyl 10 cc; of Turkey red oil 15 cc. of caustic soda solution of 34 B., and 20 grams of sodium chloride.

It is then thoroughly wrung out and developed in a diazo-solution neutralized with an alkali metalbioarbonate and containing per liter the diazo compound from 1.62 grams of 1-amino-2,5- dichlorobenzene. The 'material is rinsed and soaped at boiling temperature. A yellowishbrown dyeingw of very good fastness to washing is thus obtained.

The dyestufi has the following formula:

azo-dyestuifs obtainable according to the present invention: a

4-hydroxydiphenyl-3-carbonyl- Coupled with diazo or tetrazo compounds of: Tints .Aminobeniene. 1-amino-2,5-dichloro Yellowish brown. Aminoben ene 4-amino-3,2-dimethy1-l,l-azobenzene Orange-brown. Aminobenzene 4-ammo-4-methoxy-diphenylamine. Brown. Aminobenzene (2 mol 4,4-diamino-3,3-dichloro-diphenyl Reddish brown. Aminobenzene (2 mols) 4,4'-diaminc-3,3-dimethoxy-diphenyl Dark brown.

Aminobenmno Aminpbenzenel-am1110-2-meth0xy 1-amino-2-phenoxy-fichlorobenzene l-amino-4-benzoylamino-2,5-dichlorobenzene l-amino-Z-(4'-ehlorophenoxy)-5'chlorobenzene Green-olive.

Brown-yellow. Olive-brown.

l 2 3 4 5 6 g 9 l-amino-2-methoxy-benzone l-amino-Z-(Z',5-dichlorophenoxy)-5-chlorobenzene. Grey-brown. 10 l-amino-2-methoxy-benzene- 1-am1no-4-(2,5-dichlorophenoxy)-3-chlorobenzene Browm'sh old gold. 11 1-amino-2-methoxy-benzene l-aminoA-beuroylamino-Z5-dichlorobenzenen Yellowish-brown 12 1'-amiuo4-chloro-benzene.. 4-amino-3,2 -d1methyl-l,l'-azobenzene 've. 13 1 -amino-4' chlorobenzene l-amino-Z-(4'-chlorophenoxy) -5-chlotobenzene Green-olive. 14 1-aminoA-chloro-benzene.- l-amino-2,4,5-trichlor0benzene Brown. 15 l-amino-4 -ch1orobenzeue l-aminoA-nitronaphthalene Reddish brown. 16 2'-an1iu0-naphthalene (2 mols). 4,4-diamino-3,3-dichlor0-dip Brown. 17 2-amino-naphthalene 1-amino-2-phenoxy-5-chloro-benzen Green-olive. 18 1 -amino-uaphthalenel-amiu 0-2,5-d1chlorobenzene Olive-brown 19 l-amino-Z-methyl-i-nitro-benze Black. 20 4-amino-3,2-dimothyl-l,l'-azo-benz Yellowish brown. 21 l-amino-l-benzoylamino3-methoxy-6-c Yellow-brown. 22 1-amino-2,5-dichloro-b enzene- Brown. 23 l-amino-2-phenoxy-S-chloro-benzen Dark brown-olive. 24 l-BminO-i-nitlO-"nnhfhalenn I Brown. 25 l-amino-4-methyl-benzene l-amino-Z,fi-dichloro-benzene Brown. 26 l -amino-4-methyl-beuzene l-amino-2-phenoxy-5-chloro-benzene. Dark olive. 27 1'-amlno-3-methyl henzene l-amino-2,5-dichloro-benzone Brown. 28 1-s1niuo-3-methyl-benzene l-amino-2-phenoxy-5-chloro-benzene Dark olive. 29 1-amino-3-nitro-benzene 1-amino-2-phenoxy-5-chlor0-benzene a, Green-olive. 3D l'-ammo-3-nitro-benzene 1-amino-2-(2,5-dichloro-phenoxy)-5-ch1oto-b nze Green-olive.

bis-( l-hydroxy-diphenyl-3-carbonyl)- Coupled with 2 mols of the diazo compound of: Tints 31 4, 4-diamino-3', 3"-dimethcxy-diphenyl l-amino-2-phenoxy-d-chloro-beuzeno Brown. 32 4, 4-diamino-3, 3-dimethoxy-diphenyl. 1-amin0-2-chloro-4-mtro-benzene. Dark brown. 33 4, 4-diamino-3, 3"-dimethoxy-diphenyl 1am no4-111ethyl-2-n1tro-benzene- Dark brown. 34' 4, 4-diamino%', 3"-dimethoxy-diphenyl 1-am1no-2-methoxy-4-mtro-benrene Dark olive. 35 4, 4-diamino-3, 3-dimethoxy-diphenyl l-amino-2-(2, 5-d1chloro-pheuoxy)-5-chl0r0-benzene Yellowish brown. 36 4, 4-diamino-3, 3-dimethoxy-diphenyl l-amino-4-benzoylammo-2, 5-dichloro-benzene- Yellowish brown. 37 4, 4"-diamino-3, 3-dimethoxy-diphenyl 1-amino-3-methyl-2, 4-dich1oro-benzene Yellowish brown. 38 1, 4'-diamino-benzen0 l-amino-2-phenoxy-5-chloro-benzene. Olive-brown. 39 l, 4-diamino-benzene- 1-amino-2-phenylsuli0uyl-benzeue Red-brown. 40 1', 4-diamino-benzene. l-amino-2-chloro-5;tr1flu0romethylbenzene Yellowish brown. 41 4', 4-diamino-stilbene l-amino-authi aq Grey-brown. 42 1', 5'-diamino-naphthalene 4-amino-2, 5-d1metho:gy4-mtro-azo-benzene Dark brown. 43 3', 6-diamino-carbazo1e l-am1no-4-benzWlnmmo-2, 5-d1ethoxybenzene R g d d i s h gr 0 yrown. 44 3' 6-diamino-carbazole 1-amino-2-methyl-5-chloro-benzene Brown.

Since an object of the present invention is to luble in water or alkalies and to tend to depreciate the fastness of the dyestuffs to alkalies. Substituents of this kind are, for instance, the sulfonic acid and the carboxylic acid group.

We claim:

1. The water-insoluble azo-dyestufis of the following general formula:

OH R2 wherein n means the number 1 or 2, R1 stands for or anthraquinone series and R2 stands for a radiradical of the benzene, naphthalene, diphenyl cal of the benzene, naphthalene, diphenyl or carbazole series, yielding, when produced on the fiber, in general brown and olive-green dyeings of good fastness properties.

2. The water-insoluble azo-dyestufis of the following general formula:

wherein R1 stands for a radical of the benzene, naphthalene, diphenyl or anthraquinone series and R2 stands for a radical of the benzene series,

lowing general formula:

yielding, when produced on the fiber, in general brown and olive-green dyeings of good fastness properties.

3. The water-insoluble azo-dyestuffs of the fol- N=NR1 (BONE-R1 wherein R1 and R2 stand for radicals of the henzene series, yielding, when produced 'on the fiber, in general brown and olive-green dyelngs of good fastness properties.

4. The water-insoluble azo-dyestuff of the following formula:

OCH:

GONH

yielding, when produced on the fiber, yellowbrowndyeings of good fastness properties.

5. The water-insoluble azo-dyestufi of the following formula:

yielding, when produced on the fiber, dark olive dyeings of good fastness properties.

6. The water-insoluble azo-dyestufi of the following formula:

IF=N

ONH Cl yielding, when produced on the fiber, dark olive 15 dyeings of good fastness properties.

'7. Fiber dyed with the azo-dyestuffs as claimed in claim 1.

8. Fiber dyed with the azo-dyestuffs as claimed in claim 2.

9. Fiber dyed with the azo-dyestufis as claimed in claim 3.

10. Fiber dyed with the azo-dyestufi as claimed in claim 4.

11. Fiber dyed with the azo-dyestufi as claimed in claim 5.

12. Fiber dyed with the azo-dyestufi as claimed in claim 6.

OSKAR HALLER. HEINRICH MORSCHEL. 

